Azo dyes, their preparation and their use

ABSTRACT

Azo dyes comprising at least one structural unit of the formula (1) ##STR1## The azo dyes according to the invention are particularly suitable for dyeing cotton and wool and produce dyeings with good allround properties.

The present invention relates to novel azo dyes, processes for theirpreparation and their use.

The practice of dyeing has recently lead to increased requirementsregarding the quality of the dyeings and the profitability of the dyeingprocess. There consequently continues to be a demand for novel, readilyaccessible dyes which have good properties, in particular in respect ofapplication.

In the case of fibre-reactive dyes, those dyes, for example, which havean adequate substantivity and at the same time a good ease of washingoff unfixed portions are required nowadays. They should furthermore havea good tinctorial yield and a high reactivity, and in particular dyeingswith high degrees of fixing should be delivered. These requirements arenot met with regard to all the properties by the known dyes.

The present invention is therefore based on the object of discoveringnovel azo dyes, in particular for dyeing and printing fibre materials,which have the qualities characterized above to a high degree. Theyshould produce dyeings with good allround properties, for example lightand wet fastness properties.

The present invention thus relates to azo dyes containing at least onestructural unit of the formula (1) ##STR2## The azo dyes according tothe invention can belong to various classes of dye, according to theirtinctorial use. These classes of dye are described, for example, inVenkataraman "The Chemistry of Synthetic Dyes" Volume 1, pages 268-303,Academic Press, New York, London 1952 and Volume 6, pages 1-4, AcademicPress, New York, London 1972. The azo dyes according to the inventionare preferably acid, direct or reactive dyes for dyeing cotton, wool,leather, paper and wood, and in particular reactive dyes for dyeingcotton and wool, i.e. they contain at least one, and preferably at leasttwo, fibre-reactive groups and are capable of reacting with the hydroxylgroups of cellulose or with the reactive centres of natural andsynthetic polyamides to form covalent chemical bonds.

The azo dyes according to the invention preferably have the formula (2),(3) or (4) ##STR3## in which A is oxygen, sulfur or a radical --NR'--and R' is hydrogen or C₁ -C₁₂ alkyl which is substituted orunsubstituted or may be interrupted by oxygen,

B is an aliphatic or aromatic bridge member,

D₁, D₂ and D₃ independently of one another are each the radical of adiazo component of the benzene or naphthalene series,

D₄ is the radical of an aromatic tetrazo component and

R is hydrogen or an aliphatic or aromatic radical, or the radicals R andR', together with the nitrogen atom, form a heterocyclic radical.

C₁ -C₁₂ Alkyl, preferably C₁ -C₆ alkyl, and in particular C₁ -C₄ alkyl,as R' which is substituted or unsubstituted or may be interrupted byoxygen is straight-chain or branched and is, for example, methyl, ethyl,n- or isopropyl, n-, iso-, sec- or tert-butyl, n-pentyl, neo-pentyl,n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.The alkyl radicals mentioned can be interrupted by 1, 2 or 3 oxygenatoms and are unsubstituted or substituted by C₂ -C₄ alkanoylamino, forexample acetylamino or propionylamino; C₁ -C₄ alkoxy, for examplemethoxy or ethoxy; hydroxyl; sulfo; sulfato; carboxyl; cyano; orcarbamoyl, sulfamoyl, β-sulfatoethylsulfonyl or β-chloroethylsulfonyl.Preferred substituents of the alkyl radicals R' are hydroxyl, sulfo,carboxyl or sulfato, in particular hydroxyl or sulfato, and especiallyhydroxyl. Examples of the substituted alkyl radicals and the alkylradicals interrupted by oxygen are: β-hydroxyethyl,2-(β-hydroxyethoxy)ethyl, 2-[2-(β-hydroxyethoxy)ethoxy]ethyl,2-(β-chloroethylsulfonyl)ethyl, 2-(β-sulfatoethylsulfonyl)ethyl,β-sulfatoethyl, β-sulfoethyl, carboxymethyl or β-carboxyethyl.

R' is preferably hydrogen.

An aliphatic bridge member B is, for example, a C₂ -C₁₂ alkyleneradical, in particular a C₂ -C₆ alkylene radical, which can beinterrupted by 1, 2 or 3 members from the group consisting of --NH--,--N(CH₃)-- and, in particular, --O-- and is unsubstituted or substitutedby hydroxyl, sulfo, sulfato, cyano or carboxyl. Preferred substituentsof the alkylene radicals B are hydroxyl, sulfo or sulfato, in particularhydroxyl.

Aliphatic bridge members B are furthermore, for example, C₅ -C₉cycloalkylene radicals, such as, in particular, cyclohexylene radicals.The cycloalkylene radicals mentioned can be unsubstituted or substitutedby C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, sulfo, halogen orcarboxyl, in particular by C₁ -C₄ alkyl. Aliphatic bridge members B arefurthermore methylene-cyclohexylene, ethylene-cyclohexylene ormethylene-cyclohexylene-methylene radicals which are unsubstituted orsubstituted in the cyclohexylene ring by C₁ -C₄ alkyl, in particularmethyl.

An aromatic bridge member B is, for example, C₁ -C₆ alkylenephenylene,for example methylenephenylene, C₁ -C₄ alkylenephenylene-C₁ -C₄alkylene, for example methylenephenylenemethylene, or phenylene whichare unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄alkanoylamino, sulfo, halogen or carboxyl, or a radical of the formula##STR4## in which the benzene rings I and II are unsubstituted orsubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, sulfo,halogen or carboxyl and L is the direct bond or a C₂ -C₁₀ alkyleneradical, which can be interrupted by 1, 2 or 3 oxygen atoms, or L is abridge member of the formula --CH═CH--, --N═N--, --NH--, --CO--,--NH--CO--, --NH--SO₂ --, --NH--CO--NH--, --O--, --S-- or --SO₂ --. Thearomatic bridge members B mentioned are preferably unsubstituted orsubstituted by sulfo.

If A is oxygen in the dye of the formula (3), an aromatic bridge memberB is preferably a radical of the formula (5) in which the benzene ringsI and II are unsubstituted or substituted as defined above and L is asdefined and preferred above. Preferably, the benzene rings I and II areunsubstituted and L is isopropylene.

B is preferably a C₂ -C₁₂ alkylene radical, in particular a C₂ -C₆alkylene radical, which can be interrupted by 1, 2 or 3 members --O--and is unsubstituted or substituted by hydroxyl or sulfato.

Substituents of the radicals D₁, D₂ and D₃ are the substituentscustomary for azo dyes. Examples are the following: C₁ -C₄ alkyl, whichis to be understood as meaning methyl, ethyl, n- or iso-propyl, n-,iso-, sec- or tert-butyl; C₁ -C₄ alkoxy, which is to be understood asmeaning methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- ortert-butoxy; hydroxy-C₁ -C₄ alkoxy; phenoxy; C₂ -C₆ -alkanoylamino whichis unsubstituted or substituted in the alkyl moiety by hydroxyl or C₁-C₄ alkoxy, for example acetylamino, hydroxyacetylamino,methoxyacetylamino or propionylamino; benzoylamino which isunsubstituted or substituted in the phenyl moiety by hydroxyl, sulfo,halogen, C₁ -C₄ alkyl or C₁ -C₄ alkoxy; C₁ -C₆ alkoxycarbonylamino whichis unsubstituted or substituted in the alkyl moiety by hydroxyl, C₁ -C₄alkyl or C₁ -C₄ alkoxy; phenoxycarbonylamino, which is unsubstituted orsubstituted in the phenyl moiety by hydroxyl, C₁ -C₄ alkyl or C₁ -C₄alkoxy; amino; N--C₁ -C₄ alkyl- or N,N-di-C₁ -C₄ alkylamino which areunsubstituted or substituted in the alkyl moiety by hydroxyl, C₁ -C₄alkoxy, carboxyl, cyano, halogen, sulfo, sulfato, phenyl or sulfophenyl,for example methylamino, ethylamino, N,N-dimethylamino,N,N-diethylamino, β-cyanoethylamino, β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, γ-sulfo-n-propylamino,β-sulfatoethylamino, N-ethyl-N-(3-sulfobenzyl)amino orN-(β-sulfoethyl)-N-benzylamino; cyclohexylamino; N-phenylamino or N-C₁-C₄ alkyl-N-phenylamino which are unsubstituted or substituted in thephenyl moiety by nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, carboxyl, halogenor sulfo; C₁ -C₄ alkoxycarbonyl, for example methoxy- or ethoxycarbonyl;tifluoromethyl; nitro; cyano; halogen, which is generally to beunderstood as meaning, for example, fluorine, bromine or, in particular,chlorine; ureido; hydroxyl; carboxyl; sulfo; sulfomethyl; carbamoyl;carbamido; sulfamoyl; N-phenylsulfamoyl or N--C₁ -C₄alkyl-N-phenylsulfamoyl which are unsubstituted or substituted in thephenyl moiety by sulfo or carboxyl; and methyl- or ethylsulfonyl.

Fibre-reactive radicals are also possible substituents of the radicalsD₁, D₂ and D₃.

Fibre-reactive radicals are to be understood as meaning those which arecapable of reacting with the hydroxyl groups of cellulose, the amino,carboxyl, hydroxyl and thiol groups in wool and silk, or with the aminoand possibly carboxyl groups of synthetic polyamides, to form covalentchemical bonds. The fibre-reactive radicals are as a rule bonded to thedye radical directly or via a bridge member. Suitable fibre-reactiveradicals are, for example, those which contain at least one substituentwhich can be split off on an aliphatic, aromatic or heterocyclicradical, or in which the radicals mentioned contain a radical which iscapable of reaction with the fibre material, for example a vinylradical.

A fibre-reactive radical contained in D₁, D₂ and D₃ preferably has theformula (6a), (6b), (6c), (6d), (6e), (6f) or (6g)

    --SO.sub.2 --Y                                             (6a),

    --NH--CO--(CH.sub.2).sub.l --SO.sub.2 --Y                  (6b),

    --CONR.sub.2 --(CH.sub.2).sub.m --SO.sub.2 --Y             (6c),

    --NH--CO--CH(Hal)--CH.sub.2 --Hal                          (6d),

    --NH--CO--C(Hal)═CH.sub.2                              (6e), ##STR5## in which Hal is chlorine or bromine;

X₁ is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl;

T₁ independently has the meaning of X₁, or is a substituent which is notfibre-reactive or a fibre-reactive radical of the formula (7a), (7b),(7c), (7d), (7e) or (7f) ##STR6## in which R₁, R_(1a) and R_(1b)independently of one another are each hydrogen or C₁ -C₄ alkyl,

R₂ is hydrogen, C₁ -C₄ alkyl which is unsubstituted or substituted byhydroxyl, sulfo, sulfato, carboxyl or cyano or a radical ##STR7## R₃ ishydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, C₁ -C₄alkoxycarbonyl, C₁ -C₄ alkanoyloxy, carbamoyl or the group --SO₂ --Y,

alk and alk₁ independently of one another are linear or branched C₁ -C₆alkylene, arylene is a phenylene or naphthylene radical which isunsubstituted or substituted by sulfo, carboxyl, C₁ -C₄ alkyl, C₁ -C₄alkoxy or halogen,

Q is a radical --O-- or --NR₁ --, in which R₁ is as defined above,

W is a group --SO₂ --NR₂ --, --CONR₂ -- or --NR₂ CO--, in which R₂ is asdefined above,

Y is vinyl or a radical --CH₂ --CH₂ --U and U is a group which can besplit off under alkaline conditions,

Y₁ is a group --CH(Hal)--CH₂ --Hal or --C(Hal)═CH₂ and Hal is chlorineor bromine and l and m independently of one another are an integer from1 to 6 and n is the number 0 or 1; and

X₂ is halogen or C₁ -C₄ alkylsulfonyl;

X₃ is halogen or C₁ -C₄ alkyl and

T₂ is hydrogen, cyano or halogen.

A group U which can be split off under alkaline conditions is, forexample, --Cl, --Br, --F, --OSO₃ H, --SSO₃ H, --OCO--CH₃, --OPO₃H₂,--OCO--C₆ H₅, --OSO₂ --C₁ -C₄ alkyl or --OSO₂ --N(C₁ -C₄ alkyl)₂. Uis preferably a group of the formula --Cl, --OSO₃ H, --SSO₃ H,--OCO--CH₃, --OCO--C₆ H₅ or --OPO₃ H₂, in particular --Cl or --OSO₃ H,and particularly preferably --OSO₃ H.

Examples of suitable radicals Y are accordingly vinyl, β-bromo- orβ-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl,β-sulfatoethyl and β-thiosulfatoethyl. Y is preferably vinyl,β-chloroethyl or β-sulfatoethyl, and in particular vinyl orβ-sulfatoethyl.

R₁, R_(1a) and R_(1b) independently of one another are each preferablyhydrogen, methyl or ethyl, and particularly preferably hydrogen.

R₂ is preferably hydrogen or C₁ -C₄ alkyl, such as methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, andparticularly preferably hydrogen, methyl or ethyl. R₂ is particularlypreferably hydrogen.

R₃ is preferably hydrogen.

l and m independently of one another are preferably the number 2, 3 or4, and particularly preferably the number 2 or 3.

Especially preferably, l is the number 3 and m is the number 2.

Substituents T₁ which are not fibre-reactive are, for example, thefollowing radicals:

hydroxyl;

C₁ -C₄ alkoxy, for example methoxy, ethoxy, n- or isopropoxy or n-,sec-, iso- or tert-butoxy, in particular methoxy or ethoxy; the radicalsmentioned are unsubstituted or substituted in the alkyl moiety, forexample by C₁ -C₄ alkoxy, hydroxyl, sulfo or carboxyl;

C₁ -C₄ alkylthio, for example methylthio, ethylthio, n- or isopropylthioor n-butylthio; the radicals mentioned are unsubstituted or substitutedin the alkyl moiety, for example by C₁ -C₄ alkoxy, hydroxyl, sulfo orcarboxyl;

amino;

N-mono- or N,N-di-C₁ -C₆ alkylamino, preferably N-mono- or N,N-di-C₁ -C₄alkylamino; the radicals mentioned are unsubstituted, uninterrupted orinterrupted in the alkyl moiety by oxygen or substituted in the alkylmoiety, for example by C₂ -C₄ alkanoylamino, C₁ -C₄ alkoxy, hydroxyl,sulfo, sulfato, carboxyl, cyano, carbamoyl or sulfamoyl; examples areN-methylamino, N-ethylamino, N-propylamino, N,N-di-methylamino orN,N-di-ethylamino, N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino,N-2-(β-hydroxyethoxy)ethylamino,N-2-[2-(β-hydroxyethoxy)ethoxy]ethylamino, N-β-sulfatoethylamino,N-β-sulfoethylamino, N-carboxymethylamino, N-β-carboxyethylamino,N-α,β-dicarboxyethylamino, N-α,γ-dicarboxypropylamino,N-ethyl-N-β-hydroxyethylamino or N-methyl-N-β-hydroxyethylamino;

C₅ -C₇ cycloalkylamino, for example cyclohexylamino, which includes boththe unsubstituted radicals and the radicals substituted in thecycloalkyl ring, for example by C₁ -C₄ alkyl, in particular methyl, orcarboxyl;

phenylamino or N--C₁ -C₄ alkyl-N-phenylamino, which includes both theunsubstituted radicals and the radicals substituted in the phenyl ring,for example by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,carboxyl, carbamoyl, sulfo or halogen, for example 2-, 3- or4-chlorophenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or4-methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, disulfophenylaminoor 2-, 3- or 4-carboxyphenylamino;

naphthylamino which is unsubstituted or substituted in the naphthylring, for example by sulfo, preferably the radicals substituted by 1 to3 sulfo groups, for example 1- or 2-naphthylamino,1-sulfo-2-naphthylamino, 1,5-disulfo-2-naphthylamino or4,8-disulfo-2-naphthylamino; or

benzylamino which is unsubstituted or substituted in the phenyl moiety,for example by C₁ -C₄ alkyl, C₁ -C₄ alkoxy , carboxyl, sulfo or halogen.

A radical T₁ which is not fibre-reactive is preferably C₁ -C₄ alkoxy, C₁-C₄ alkylthio, hydroxyl, amino, N-mono- or N,N-di-C₁ -C₄ alkylaminowhich are optionally substituted in the alkyl moiety by hydroxyl,sulfato or sulfo, morpholino, phenylamino or N--C₁ -C₄alkyl-N-phenylamino which are unsubstituted or substituted in the phenylring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and inwhich the alkyl is unsubstituted or substituted by hydroxyl, sulfo orsulfato, or naphthylamino which is unsubstituted or substituted by 1 to3 sulfo groups.

Particularly preferred radicals T₁ which are not fibre-reactive areamino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethy-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino,2-, 3- or 4-sulfophenylamino or N--C₁ -C₄ -alkyl-N-phenylamino.

X₁ is preferably halogen, for example fluorine, chlorine or bromine, andparticularly preferably chlorine or fluorine.

Halogen T₂, X₂ and X₃ are, for example, fluorine, chlorine or bromine,in particular chlorine or fluorine.

C₁ -C₄ Alkylsulfonyl X₂ is, for example, ethylsulfonyl ormethylsulfonyl, and in particular methylsulfonyl.

C₁ -C₄ alkyl X₃ is, for example, methyl , ethyl, n- or iso-propyl or n-,iso or tert-butyl, and in particular methyl.

X₂ and X₃ independently of one another are preferably chlorine orfluorine.

T₂ is preferably cyano or chlorine.

Hal is preferably bromine.

alk and alk₁ independently of one another are, for example, a methylene,ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexyleneradical or branched isomers thereof.

alk and alk₁ independently of one another are preferably each a C₁ -C₄alkylene radical, and particularly preferably an ethylene radical orpropylene radical.

arylene is preferably a 1,3- or 1,4-phenylene radical which isunsubstituted or substituted, for example by sulfo, methyl, methoxy orcarboxyl, and particularly preferably an unsubstituted 1,3- or1,4-phenylene radical.

Q is preferably --NH-- or --O--, and particularly preferably --O--.

W is preferably a group of the formula --CONH-- or --NHCO--, inparticular a group of the formula --CONH--.

n is preferably the number 0.

The reactive radicals of the formulae (7a) to (7f) are preferably thosein which W is a group of the formula --CONH--, R₁, R₂ and R₃ are eachhydrogen, Q is the radical --O-- or --NH--, alk and alk₁ independentlyof one another are each ethylene or propylene, arylene is phenylenewhich is unsubstituted or substituted by methyl, methoxy, carboxyl orsulfo, Y is vinyl or β-sulfatoethyl, Y₁ is --CHBr--CH₂ Br or --CBr═CH₂and n is the number 0.

A fibre-reactive radical contained in D₁, D₂ and D₃ is particularlypreferably a radical of the formula (6a), (6c), (6d), (6e) or (6f), inwhich Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromine, R₂and R_(1a) are hydrogen, m is the number 2 or 3, X₁ is halogen, T₁ is C₁-C₄ alkoxy, C₁ -C₄ alkylthio, hydroxyl, amino, N-mono- or N,N-di-C₁ -C₄alkylamino which are unsubstituted or substituted in the alkyl moiety byhydroxyl, sulfato or sulfo, morpholino, phenylamino or N--C₁ -C₄alkyl-N-phenylamino which are unsubstituted or substituted in the phenylring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and inwhich the alkyl is unsubstituted or substituted by hydroxyl, sulfo orsulfato, or naphthylamino which is unsubstituted or substituted by 1 to3 sulfo groups, or a fibre-reactive radical of the formula (7a'), (7b'),(7c'), (7d') or (7f')

    --NH--(CH.sub.2).sub.2-3 --SO.sub.2 Y                      (7a'),

    --NH--(CH.sub.2).sub.2-3 --O--(CH.sub.2).sub.2-3 --SO.sub.2 Y(7b'), ##STR8## in particular (7c') or (7d'), in which Y is as defined above and

Y₁ is a group --CH(Br)--CH₂ --Br or --C(Br)═CH₂,

In the case of the radicals of the formulae (7a') and (7b'), Y ispreferably β-chloroethyl. In the case of the radicals of the formulae(7c') and (7d'), Y is preferably vinyl or β-sulfatoethyl.

A particular embodiment of the present invention relates to dyes inwhich a radical contained in D₁, D₂ and D₃ has the formula (6h) ##STR9##in which R_(1a) and X₁ are as defined and preferred above and

T₃ is a monoazo- or disazoamino radical of the formula (8) or (9)

    D--N═N--(M--N═N).sub.u --K--NR.sub.1 --            (8)

or

    --NR.sub.1 --D--N═N--(M--N═N).sub.u --K            (9)

in which

D is the radical of a diazo component of the benzene or naphthaleneseries,

M is the radical of a middle component of the benzene or naphthaleneseries,

K is the radical of a coupling component of the benzene, naphthalene,pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series,

R₁ is as defined and preferred above and

u is the number 0 or 1, where D, M and K can carry the substituentscustomary in azo dyes.

The term "substituents customary in azo dyes" means both fibre-reactivesubstituents and substituents which are not fibre-reactive, for examplethe substituents defined above for D₁, D₂ and D₃.

Substituents for D, M and K in T₃ which are not fibre-reactive arepreferably C₁ -C₄ alkyl or C₁ -C₄ alkoxy which are unsubstituted orfurther substituted by hydroxyl, sulfo or sulfato, halogen, carboxyl,sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino,ureido, hydroxyl, sulfomethyl, C₂ -C₄ alkanoylamino, benzoylamino whichis unsubstituted or substituted in the phenyl ring by C₁ -C₄ alkyl, C₁-C₄ alkoxy, halogen or sulfo or phenyl which is unsubstituted orsubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxyl or sulfo.

The monoazo- or disazoamino radicals of the formula (8) or (9)preferably contain at least one sulfo group.

Preferred monoazo- or disazoamino radicals T₃ are the radicals of theformula (10a), (10b), (10c), (10d), (10e), (10f), (10g), (10h), (10i),(10j), (10k), (10l), (10m), (10n), (10o) or (10p) ##STR10## in which(R₄)₀₋₃ is 0 to 3 identical or different substituents from the groupconsisting of C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxyl and sulfo,

(R₅)₀₋₃ is 0 to 3 identical or different substituents from the groupconsisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, C₁ -C₄ alkyl, C₁ -C₄ alkoxy which is unsubstituted orsubstituted by hydroxyl, sulfato or C₁ -C₄ alkoxy, amino, C₂ -C₄alkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, C₁ -C₄alkylsulfonylamino and sulfo and

Z₁ is a radical of the formula (6a), (6c), (6d), (6e), (6f) or (6g),preferably (6a), (6c), (6d) or (6e), and in particular (6a), where theradicals mentioned are as defined and preferred above, ##STR11## inwhich R₆ is C₂ -C₄ alkanoyl or benzoyl, ##STR12## in which (R₇)₀₋₃ is 0to 3 identical or different substituents from the group consisting of C₁-C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxyl and sulfo, ##STR13## inwhich R₈ and R₁₀ independently of one another are hydrogen, C₁ -C₄ alkylor phenyl and R₉ is hydrogen, cyano, carbamoyl or sulfomethyl, ##STR14##in which (R₄)₀₋₃, (R₅)₀₋₃ and (R₇)₀₋₃ in each case are as defined above,

(R₁₁)₀₋₃ and (R₁₂)₀₋₃ independently of one another are 0 to 3 identicalor different substituents from the group consisting of C₁ -C₄ alkyl, C₁-C₄ alkoxy, halogen, carboxyl and sulfo and Z₁ is as defined andpreferred above.

The numbers on the naphthyl rings of the radicals of the formulae (10a),(10b), (10c), (10d), (10e), (10g) and (10h) identify the possiblebonding positions.

(R₄)₀₋₃ in the disazoamino radicals of the formulae (10n) and (10p) ispreferably 0 to 3 sulfo groups.

Particularly preferred monoazo- or disazoamino radicals T₃ are theradicals of the formula (10a), (10b), (10d), (10e), (10f), (10k) or(10m), in particular (10b), (10k) or (10m).

Preferably, a radical of the formula (6h) in which R_(1a), X₁ and T₃ areas defined and preferred above is contained in only one of the radicalsD₁, D₂ and D₃, in particular in D₁.

Radicals D₁, D₂ and D₃ of a substituted or unsubstituted diazo componentof the benzene or naphthalene series independently of one another are,for example, phenyl or naphthyl, which is unsubstituted or substituted,for example by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, sulfo, nitro,carboxyl or a fibre-reactive radical of the formulae (6a), (6b), (6c),(6d), (6e), (6f) or (6g), in particular (6a), (6c), (6d), (6e) or (6f),in which the fibre-reactive radicals mentioned are as defined andpreferred above.

Radicals D₁, D₂ and D₃ of a substituted or unsubstituted diazo componentof the benzene or naphthalene series independently of one another alsoinclude monoazo radicals, for example those of the formula (11) or (12)

    --D*--N═N--K*                                          (11)

or

    D*--N═N--K**--                                         (12),

preferably of the formula (12), in which D* is the radical of a diazocomponent of the benzene or naphthalene series, K* is the radical of acoupling component of the benzene, naphthalene, pyrazolone,6-hydroxypyrid-2-one or acetoacetic acid arylamide series and K** is theradical of a coupling component of the benzene or naphthalene series,where D*, K* and K** can carry substituents customary in azo dyes.

Substituents which are not fibre-reactive D*, K* and K** are preferablyC₁ -C₄ alkyl or C₁ -C₄ alkoxy which are unsubstituted or furthersubstituted by hydroxyl, C₁ -C₄ alkoxy, sulfo or sulfato, halogen,carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl,amino, ureido, hydroxyl, sulfomethyl, C₂ -C₄ alkanoylamino, C₁ -C₄alkylsulfonylamino, benzoylamino which is unsubstituted or substitutedin the phenyl ring by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen or sulfo orphenyl which is unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄alkoxy, halogen, carboxyl or sulfo.

Fibre-reactive substituents for D*, K* and K** are preferably theradicals of the formulae (6a), (6c), (6d), (6e) or (6f), in particular(6a), in which the radicals mentioned are as defined and preferredabove.

The monoazo radicals of the formula (11) or (12) preferably contain atleast one sulfo group.

Preferred monoazo radicals D₁, D₂ and D₃ of the formula (12) are theradicals of the formula (12a), (12b), (12c), (12d), (12e), (12f), (12g),(12h), (12i) or (12j) ##STR15## in which (R₄)₀₋₃ is 0 to 3 identical ordifferent substituents from the group consisting of C₁ -C₄ alkyl, C₁ -C₄alkoxy, halogen, carboxyl and sulfo and Z₁ is a fibre-reactive radicalof the formula (6a), (6c), (6d), (6e), (6f) or (6g), preferably (6a),(6c), (6d) or (6e), and in particular (6a), in which the fibre-reactiveradicals mentioned are as defined and preferred above, ##STR16## inwhich (R₄)₀₋₃ is as defined above, (R'₅)₀₋₃ is 0 to 3 identical ordifferent substituents from the group consisting of halogen, nitro,cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ -C₄ alkyl, C₁ -C₄alkoxy which is unsubstituted or substituted by hydroxyl, sulfato or C₁-C₄ alkoxy, amino, C₂ -C₄ alkanoylamino, ureido, hydroxyl, carboxyl,sulfomethyl, C₁ -C₄ alkylsulfonylamino, sulfo and a fibre-reactiveradical of the formula (6f), in which the radicals R_(1a), T₁ and X₁ areas defined and preferred above, and Z₁ is as defined and preferredabove.

The numbers on the naphthyl rings of the radicals of the formulae (12a),(12b), (12e) and (12f) identify the possible bonding positions.

The radicals D₁, D₂ and D₃ in the dyes of the formulae (2) or (3)according to the invention and the radicals D₁ and D₂ in the dyes of theformula (4) according to the invention are identical or are notidentical.

An aromatic tetrazo component D₄ is, for example, phenylene ornaphthylene which are unsubstituted or substituted by C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₂ -C₄ alkanoylamino, sulfo, halogen or carboxyl, or aradical of the formula (5), where the radical of the formula (5) is asdefined above.

An aromatic tetrazo component D₄ is also a radical of the formula (5')##STR17##

Preferably, D₄ is a naphthylene which is substituted by 1 to 3,preferably 2, sulfo groups, a radical of the formula (5') or a radicalof the formula (5), in which the benzene rings I and II areunsubstituted or substituted by 1 or 2 sulfo groups and L is a directbond, a C₂ -C₄ alkylene radical or a bridge member of the formula--CH═CH--, --NH--, --CO--, --NH--CO--, --NH--SO₂ --, --NH--CO--NH--,--O--, --S-- or --SO₂ --.

An aliphatic radical R is, for example, the radicals defined above forC₁ -C₁₂ alkyl R' which is substituted or unsubstituted or interrupted byoxygen. Further examples of R are the following radicals:2,5-di-(β-chloroethylsulfonyl)pentyl,2-[2-(β-chloroethylsulfonyl)ethoxy]ethyl or2-[2-(β-sulfatoethylsulfonyl)ethoxy]ethyl.

Aliphatic radicals R are furthermore, for example, C₅ -C₇ cycloalkylradicals, such as, in particular, cyclohexyl radicals. The cycloalkylradicals mentioned can be unsubstituted or substituted by C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, sulfo, halogen or carboxyl, inparticular by C₁ -C₄ alkyl. Aliphatic radicals R are furthermoremethylene-cyclohexyl or ethylene-cyclohexyl radicals which areunsubstituted or substituted in the cyclohexyl ring by C₁ -C₄ alkyl, inparticular methyl.

An aromatic radical R is, for example, phenyl or naphthyl which areunsubstituted or substituted, which include both the unsubstitutedradicals and the radicals substituted by C₁ -C₄ alkyl, for examplemethyl or ethyl; C₁ -C₄ alkoxy, for example methoxy or ethoxy; C₂ -C₄alkanoylamino; carboxyl; carbamoyl; sulfo or halogen, for examplechlorine or bromine; or a fibre-reactive radical of the formula (6a),(6b), (6c), (6d), (6e), (6f) or (6g), where the fibre-reactive radicalsof the formulae (6a), (6b), (6c), (6d), (6e), (6f) and (6g) are asdefined and preferred above. Examples are the following radicals: o-, m-or p-chlorophenyl, o-, m- or p-methylphenyl, o-, m- or p-methoxyphenyl,o-, m- or p-sulfophenyl, disulfophenyl, o-, m- or p-carboxyphenyl, 1- or2-naphthyl, 1-sulfo-2-naphthyl, 1,5-disulfo-2-naphthyl,4,8-disulfo-2-naphthyl or 4-(β-sulfatoethylsulfonyl)phenyl.

Substituted or unsubstituted phenyl or naphthyl R furthermore is, forexample, a monoazo or disazo radical of the formula (13) or (14)

    D--N═N--(M--N═N).sub.u --K--                       (13)

or

    --D--N═N--(M--N═N).sub.u --K                       (14),

in which D, M, K and u are as defined above under the formulae (8) and(9).

Monoazo radicals R are, for example, the radicals of the formula (10a),(10b), (10c), (10d), (10e), (10f), (10g), (10h), (10i), (10j), (10k),(10l), (10m), (10n), (10o) or (10p) defined above, if the group --NH--in the particular formula is replaced by a direct bond.

A heterocyclic radical formed by the radicals R and R', together withthe nitrogen atom, is, for example, morpholine.

In a preferred embodiment of the azo dyes of the formula (2), (3) or (4)according to the invention, A is oxygen or a radical --NR'--.

If A in the dyes of the formula (2) or (4) according to the invention isa radical --NR'--, R' is preferably hydrogen and R is preferablyhydrogen, a C₁ -C₄ alkyl which is unsubstituted or substituted byhydroxyl, sulfo, carboxyl or sulfato, in particular hydroxyl or sulfato,and especially hydroxyl, or 2-(β-sulfatoethylsulfonyl)ethyl.

If A in the dyes of the formula (2) or (4) according to the invention isoxygen, R is preferably hydrogen or C₁ -C₄ alkyl which is unsubstitutedor substituted by hydroxyl, and in particular hydrogen.

In the dyes of the formula (3) according to the invention, A ispreferably a radical --NR'--, in which R' is hydrogen, methyl or ethyl,and especially hydrogen.

In a particularly preferred embodiment of the azo dyes of the formula(2) or (4) according to the invention, A is oxygen and R is hydrogen.

The azo dyes of the formula (2) or (4) according to the invention, andin particular of the formula (2), are preferred.

The radicals D₁, D₂ and D₃ independently of one another are preferablyeach a radical of the formula (15) or (16) ##STR18## in which K is theradical of a coupling component of the formula (17a) or (17b) ##STR19##and Z and Z₁ independently of one another are a radical of the formula(6a), (6c), (6d), (6e) or (6f), in which

R_(1a) and R₂ are hydrogen,

Hal is bromine,

Y is vinyl, β-chloroethyl or β-sulfatoethyl,

T₁ is C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, hydroxyl, amino, N-mono- orN,N-di-C₁ -C₄ alkylamino which are unsubstituted or substituted in thealkyl moiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino orN--C₁ -C₄ alkyl-N-phenylamino which are unsubstituted or substituted inthe phenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl ormethoxy and in which the alkyl is unsubstituted or substituted byhydroxyl, sulfo or sulfato, naphthylamino which is unsubstituted orsubstituted by 1 to 3 sulfo groups, or a fibre-reactive radical of theformula (7c') or (7d') ##STR20## and Y is as defined above,

X₁ is chlorine or fluorine,

m is the number 2 or 3,

(R₄)₀₋₃ and (R₁₃)₀₋₃ independently of one another are 0 to 3 identicalor different substituents chosen from the group consisting of halogen,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, carboxyl and sulfo,

R'₅ is hydrogen, sulfo or C₁ -C₄ alkoxy which is unsubstituted orsubstituted in the alkyl moiety by hydroxyl or sulfato and

R'_(5a) is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,ureido or a radical of the formula (6f), in which radicals R_(1a), T₁and X₁ are as defined above.

C₁ -C₄ Alkyl R₄, R'_(5a) and R₁₃ independently of one another are, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl or isobutyl, preferably methyl or ethyl, and in particularmethyl.

C₁ -C₄ -Alkoxy R₄, R'₅, R'_(5a) and R₁₃ independently of one anotherare, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy orisobutoxy, preferably methoxy or ethoxy, and in particular methoxy. R'₅is unsubstituted or may be substituted in the alkyl moiety by hydroxylor sulfato.

Halogen R₄ and R₁₃ independently of one another are, for example,fluorine, chlorine or bromine, preferably chlorine or bromine, and inparticular chlorine.

C₂ -C₄ -Alkanoylamino R'_(5a) is, for example, acetylamino orpropionylamino, in particular acetylamino.

A radical R'_(5a) of the formula (6f) is preferably a radical in which

R_(1a) is hydrogen,

T₁ is amino, N-mono- or N,N-di-C₁ -C₄ alkylamino which are unsubstitutedor substituted in the alkyl moiety by hydroxyl, sulfato or sulfo,morpholino, phenylamino or N--C₁ -C₄ alkyl-N-phenylamino which areunsubstituted or substituted in the phenyl ring by sulfo, carboxyl,acetylamino, chlorine, methyl or methoxy and in which the alkyl isunsubstituted or substituted by hydroxyl, sulfo or sulfato ornaphthylamino which is unsubstituted or substituted by 1 to 3 sulfogroups and

X₁ is fluorine or chlorine.

In the radical of the coupling component of the formula (17b), the sulfogroup in the ring ii is preferably bonded in the 3- or 4-position. Ifthe ring ii contains a sulfo group, the radical of the formula (17b) ispreferably bonded to the ring ii in the 1-, 2- or 3-position. If nosulfo group is present in the ring ii, the radical of the formula (17b)is preferably bonded to the ring ii in the 2- or 3-position.

The radicals D₁, D₂ and D₃ independently of one another are particularlypreferably each a radical of the formula (15a), (15b), (15c), (15d) or(16a) ##STR21## in which R'₅ is hydrogen, sulfo or ethoxy which isunsubstituted or substituted in the alkyl moiety by hydroxyl or sulfato,

R'_(5a) is hydrogen, methyl, ethyl, methoxy, ethoxy, acetylamino,propionylamino or ureido,

(R₁₃)₀₋₂ is 0 to 2 identical or different substituents chosen from thegroup consisting of halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy and sulfo, inparticular methyl, methoxy and sulfo,

Y₁ is a group --CH(Br)--CH₂ --Br or --C(Br)═CH₂,

Y is vinyl, β-chloroethyl or β-sulfatoethyl, in particular vinyl orβ-sulfatoethyl, and

m is the number 2 or 3, in particular 2.

The numbers in the radicals of the formulae (15a), (15c) and (15d)identify the possible bonding positions of the fibre-reactive radical.

D₁, D₂ and D₃ independently of one another are in each case preferably aradical of the formula (15a), (15b) or (16a).

In the particular embodiment of the present invention defined above, inwhich a radical contained in D₁, D₂ and D₃ has the formula (6h), D₁ ispreferably a radical of the formula (18) ##STR22## in which X₁ ischlorine or fluorine, in particular chlorine, and

T₃ is a monoazo- or disazoamino radical of the formula (10a), (10b),(10d), (10e), (10f), (10k) or (10m), in which the radicals (R₄)₀₋₃,(R₅)₀₋₃, R₈, R₁₀, R₉ and (R₁₁)₀₋₃ are as defined above, and

Z₁ is a radical of the formula (6a), (6c'), (6d') or (6e')

    --SO.sub.2 --Y                                             (6a),

    --CONH--(CH.sub.2).sub.2-3 --SO.sub.2 --Y                  (6c'),

    --NH--CO--CH(Br)--CH.sub.2 --Br                            (6d')

or

    --NH--CO--C(Br)═CH.sub.2                               (6e'),

preferably (6a), in which Y is vinyl, β-chloroethyl or β-sulfatoethyl,in particular vinyl or β-sulfatoethyl; and the radicals

D₂ and D₃ independently of one another are each a radical of the formula(15a), (15b), (15c) or (15d), in which the radicals (R₁₃)₀₋₂, Y, Y₁ andm are as defined above.

Preferred dyes are those of the formula (2a) ##STR23## in which D₁, D₂and D₃ independently of one another in each case are a radical of theformula (15a), (15b), (15c), (15d) or (16a), preferably (15a), (15b) or(16a), where at least one of the radicals D₁, D₂ and D₃ contains afibre-reactive group; or

D₁ is a radical of the formula (18), in which

X₁ is chlorine and T₃ is a radical of the formula (10a), (10b), (10d),(10e), (10f), (10k) or (10m), preferably (10b), (10k) or (10m), and

D₂ and D₃ independently of one another in each case are a radical of theformula (15a), (15b), (15c) or (15d), preferably (15a) or (15b), whereat least one of the radicals D₂ and D₃ contains a fibre-reactive group.

Preferably, at least two of the radicals D₁, D₂ and D₃ in the dye of theformula (2a) contain a fibre-reactive group.

The present invention furthermore relates to a process for thepreparation of the azo dyes according to the invention, which comprisescoupling one or more than one diazotized amine together or in anydesired sequence to a compound containing at least one structural unitof the formula (19) ##STR24## such that an azo dye which contains atleast one structural unit of the formula (1) is obtained.

More than one diazotized amine means, for example, 2 or 3 diazotizedamines.

Amines which are suitable for the preparation of the azo dyes accordingto the invention are, for example, aromatic amines of the benzene ornaphthalene series which can be diazotized and are capable of couplingin accordance with processes known per se, such as are described, forexample, in Venkataraman "The Chemistry of Synthetic Dyes" Volume 1,pages 210-214 and 409-441, Academic Press, New York, London 1952.

The amines are diazotized, for example, with a nitrite, for example withan alkali metal nitrite, such as sodium nitrite, in a mineral acidmedium, for example in a hydrochloric acid medium, at temperatures of,for example, -5 to 40° C., and preferably at -5 to 10° C.

Coupling to the coupling components of the formula (19) is carried outin a manner known per se at an acid or neutral to weakly alkaline pH,for example a pH of 1 to 10, and at temperatures of, for example, -5 to40° C., preferably 0 to 30° C.

The coupling reaction is advantageously first carried out in a stronglyacid medium, for example at pH 1, and the pH of the reaction mixture isincreased slowly, for example to pH 5 to 8, as the reaction progresses.

Azo dyes of the formula (2) in which A is oxygen and R is hydrogen andD₁ =D₂ ≠D₃ or D₂ =D₃ ≠D₁ are obtained, for example, by first reactingabout 1 molar equivalent of a diazotized amine of the formula (20a)

    D.sub.1 --NH.sub.2                                         (20a)

in an acid medium with about 1 molar equivalent of a compound of theformula (19a) ##STR25## to give a compound of the formula (21a)##STR26## and allowing the compound of the formula (21a) to react at anincreased pH with about 2 molar equivalents of a diazotized amine of theformula (20b)

    D.sub.2 --NH.sub.2                                         (20b)

in which D₁ and D₂ are as defined and preferred above.

Azo dyes of the formula (2) in which A is oxygen, sulfur or a radical--NR'-- and R is an aliphatic or aromatic radical and D₁ =D₂ ≠D₃ or D₂=D₃ ≠D₁ are obtained, for example, by reacting about 1 molar equivalentof a compound of the formula (22a) ##STR27## with about 1 molarequivalent of a compound of the formula (23)

    R--AH                                                      (23)

in a manner known per se to give a compound of the formula (22b)##STR28## reducing the compound of the formula (22b) to a compound ofthe formula (19c) ##STR29## in a manner known per se and then furtherreacting the compound of the formula (19c) stepwise with the diazotizedamines of the formulae (20a) and (20b) analogously to the proceduredescribed above, where R' and R are as defined and preferred above.

Azo dyes of the formula (3) in which D₁ =D₂ ≠D₃ or D₂ =D₃ ≠D₁ areobtained, for example, by reacting about 2 molar equivalents of acompound of the formula (22a) with about 1 molar equivalent of acompound of the formula (24)

    HA--B--AH                                                  (24)

in a manner known per se to give a compound of the formula (22c)##STR30## reducing the compound of the formula (22c) to a compound ofthe formula (19d) ##STR31## in a manner known per se and then furtherreacting the compound of the formula (19d) stepwise with the equivalentamount of the diazotized amines of the formulae (20a) and (20b)analogously to the procedure described above, where A and B are asdefined and preferred above.

The conditions for the reduction of the compounds of the formulae (22b)and (22c) are advantageously chosen such that any functional groupspresent in R, R' or B are not reduced. Such selective reductionreactions are known and are widely described in the relevant literature.

Those dyes of the formulae (2) and (3) according to the invention inwhich D₁ ≠D₂ ≠D₃ can be obtained if the procedure described above isfollowed, except the equimolar amount of a mixture of, for example, twodiazotized amines D₂ --NH₂ and D₃ --NH₂ in a molar ratio of, forexample, 1:1 is used in place of a diazotized amine D₂ --NH₂. As a rule,these dyes are obtained as mixtures.

Azo dyes of the formula (4) in which A is oxygen and R is hydrogen andD₁ =D₂ are obtained, for example, by first reacting about 1 molarequivalent of a tetrazotized diamine of the formula (20c)

    H.sub.2 N--D.sub.4 --NH.sub.2                              (20c)

in a hydrochloric acid medium with about 2 molar equivalents of acompound of the formula (19a) to give a compound of the formula (21b)##STR32## and allowing the compound of the formula (21b) to react at anincreased pH with about 4 molar equivalents of a diazotized amine of theformula D₁ --NH₂, where D₁ and D₄ are as defined and preferred above.

Azo dyes of the formula (4) in which A is oxygen, sulfur or a radical--NR'-- and R is an aliphatic or aromatic radical and D₁ =D₂ areobtained, for example, if the procedure described above is followed,except that the equimolar amount of a compound of the formula (19c) isused in place of the compound of the formula (19a).

Those dyes of the formulae (4) according to the invention in which D₁≠D₂ can be obtained if the procedure described above is followed, exceptthat an equimolar amount of a mixture of, for example, two diazotizedamines D₁ --NH₂ and D₂ --NH₂ in a molar ratio of, for example, 1:1 isused in place of a diazotized amine D₁ --NH₂. As a rule, the dyes areobtained as mixtures.

The compounds of the formulae (19a), (20a), (20b), (20c), (22a), (23)and (24) are known or can be obtained in a manner known per se.

Valuable direct dyes can be obtained from the dyes according to theinvention which contain exclusively one or more halogenotriazinylradicals of the formula (6f) as the fibre-reactive radical and in whichX₁ is chlorine or fluorine and T₁ is a radical which is notfibre-reactive, by further reacting the dye with an amount equivalent tothe amount of halogenotriazinyl of, for example, a compound of theformula T₁ --H, in which T₁ is as defined above, excluding afibre-reactive radical. In particular, T₁ --H is ammonia, an amine whichis unsubstituted or substituted as defined above or morpholine. Suchreactions can be carried out by processes known per se.

The dyes according to the invention are suitable for dyeing and printingthe most diverse materials, in particular fibre materials containinghydroxyl groups or containing nitrogen. Examples are paper, silk,leather, wool, polyamide fibres and polyurethanes, and in particular alltypes of cellulosic fibre materials. Such fibre materials are, forexample, the natural cellulose fibres, such as cotton, linen and hemp,as well as pulp and regenerated cellulose. The dyes according to theinvention are also suitable for dyeing or printing fibres containinghydroxyl groups which are contained in blend fabrics, for examplemixtures of cotton with polyester fibres or polyamide fibres.

The present invention therefore furthermore relates to the use ofcompounds of the formula (1) for dyeing or printing fibre materialscontaining hydroxyl groups or containing nitrogen, in particularcontaining cotton.

The dyes according to the invention can be applied to the fibre materialand fixed to the fibre in various ways, in particular in the form ofaqueous dye solutions and printing pastes. They are suitable both forthe exhaust method and for dyeing by the padder method, can be employedat low dyeing temperatures and require only short steaming times in thepad-steam process. The degrees of fixing are high and the unfixedportions can easily be washed off, the difference between the degree ofexhaustion and degree of fixing being remarkably small, i.e. the soapingloss is very low. The dyes according to the invention are also suitablefor printing, in particular on cotton, but likewise also for printingfibres containing nitrogen, for example wool, silk or blend fabricscontaining wool.

The dyeings and prints produced with the dyes according to theinvention, in particular the reactive dyes, have a high colour strengthand a high fibre-dye bond stability both in the acid and in the alkalinerange, and furthermore a good fastness to light and very goodwet-fastness properties, such as fastness to washing, water, sea water,crossdyeing and perspiration. Dyeings which are level over the fibre andsurface are obtained.

The following examples serve to illustrate the invention. Temperaturesare stated in degrees Celsius, parts are parts by weight and percentagedata relate to % by weight, unless noted otherwise. Parts by weight bearthe same relation to parts by volume as the kilogram to the liter.

EXAMPLE 1 17.3 parts of an amine of the formula D₁₀ --NH₂, in which D₁₀is a radical of the formula ##STR33## are introduced into 215 parts ofwater and the mixture is stirred thoroughly. 25 parts of a 4N sodiumnitrite solution are added to the resulting solution at 0° C. and 20parts of concentrated hydrochloric acid are then slowly added dropwiseat 0 to 5° C. The mixture is stirred at this temperature for 1 hour.EXAMPLE 2 56.2 parts of an amine of the formula D₁₁ --NH₂, in which D₁₁is a radical of the formula ##STR34## are introduced into 220 parts ofwater and the mixture is stirred thoroughly. First 50 parts of a 4Nsodium nitrite solution and then 90 parts of a 31% naphthalenesulfonicacid solution are added to the resulting suspension at 10° C. Themixture is then stirred at 15 to 20° C. for 3 hours. EXAMPLES 3 to 33

The diazo compounds of the amines listed in Table 1 can be preparedanalogously to the procedure described in Examples 1 or 2 if anequimolar amount of the amines of the formula D_(xy) --NH₂ listed inTable 1 is used in place of the amines of the formula D₁₀ --NH₂ or D₁₁--NH₂ mentioned in Examples 1 or 2.

                                      TABLE 1                                     __________________________________________________________________________         Amine                                                                                         Exp. D                                                                       .sub.xy -NH.sub.2 D.sub.xy                                __________________________________________________________________________      3 D.sub.12 -NH.sub.2 D.sub.12 =                                                                   #STR35##                                                   - 4 D.sub.13 -NH.sub.2 D.sub.13 =                                                                #STR36##                                                   - 5 D.sub.14 -NH.sub.2 D.sub.14 =                                                                #STR37##                                                   - 6 D.sub.15 -NH.sub.2 D.sub.15 =                                                                #STR38##                                                   - 7 D.sub.16 -NH.sub.2 D.sub.16 =                                                                #STR39##                                                   - 8 D.sub.17 -NH.sub.2 D.sub.17 =                                                                #STR40##                                                   - 9 D.sub.18 -NH.sub.2 D.sub.18 =                                                                #STR41##                                                   - 10 D.sub.19 -NH.sub.2 D.sub.19 =                                                               #STR42##                                                   - 11 D.sub.20 -NH.sub.2 D.sub.20 =                                                               #STR43##                                                   - 12 D.sub.21 -NH.sub.2 D.sub.21 =                                                               #STR44##                                                   - 13 D.sub.22 -NH.sub.2 D.sub.22 =                                                               #STR45##                                                   - 14 D.sub.23 -NH.sub.2 D.sub.23 =                                                               #STR46##                                                   - 15 D.sub.24 -NH.sub.2 D.sub.24 =                                                               #STR47##                                                   - 16 D.sub.25 -NH.sub.2 D.sub.25 =                                                               #STR48##                                                   - 17 D.sub.26 -NH.sub.2 D.sub.26 =                                                               #STR49##                                                   - 18 D.sub.27 -NH.sub.2 D.sub.27 =                                                               #STR50##                                                   - 19 D.sub.28 -NH.sub.2 D.sub.28 =                                                               #STR51##                                                   - 20 D.sub.29 -NH.sub.2 D.sub.29 =                                                               #STR52##                                                   - 21 D.sub.30 -NH.sub.2 D.sub.30 =                                                               #STR53##                                                   - 22 D.sub.31 -NH.sub.2 D.sub.31 =                                                               #STR54##                                                   - 23 D.sub.32 -NH.sub.2 D.sub.32 =                                                               #STR55##                                                   - 24 D.sub.33 -NH.sub.2 D.sub.33 =                                                               #STR56##                                                   - 25 D.sub.34a -NH.sub.2 -D.sub.34r -NH.sub.2 D.sub.34a -D.sub.34r =                             #STR57##                                                   -                                                                          T.sub.1:                                                                        25a D.sub.34a -NH.sub.2 D.sub.34a                                                                 #STR58##                                                   - 25b D.sub.34b -NH.sub.2 D.sub.34b                                                              #STR59##                                                   - 25c D.sub.34c -NH.sub.2 D.sub.34c                                                              #STR60##                                                   - 25d D.sub.34d -NH.sub.2 D.sub.34d                                                              #STR61##                                                   -                                                                          25e  D.sub.34e -NH2                                                                         D.sub.34e  --NHCH.sub.2 CH.sub.2 OH                               25f D.sub.34f -NH.sub.2 D.sub.34f  --N(CH.sub.2 CH.sub.2 OH).sub.2            25g D.sub.34g -NH.sub.2 D.sub.34g                                                                 #STR62##                                                   - 25h D.sub.34h -NH.sub.2 D.sub.34h                                                              #STR63##                                                   -                                                                          25i  D.sub.34i -NH.sub.2                                                                    D.sub.34i --NH--(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH       25j D.sub.23j -NH.sub.2 D.sub.34j --NHCH.sub.2 CH.sub.2 SO.sub.3 H            25k D.sub.34k -NH.sub.2 D.sub.34k                                                                 #STR64##                                                   - 25l D.sub.34i -NH.sub.2 D.sub.34l                                                              #STR65##                                                   -                                                                          25m  D.sub.34m -NH.sub.2                                                                    D.sub.34m --NH--(CH.sub.2).sub.2 --SO.sub.2 --(CH.sub.2).sub                  .2 --Cl                                                           25n D.sub.34n -NH.sub.2 D.sub.34n --NH--(CH.sub.2).sub.2 --O--(CH.sub.2)                  .sub.2 --SO.sub.2 --(CH.sub.2).sub.2 --Cl                         25o D.sub.34o -NH.sub.2 D.sub.34o                                                                 #STR66##                                                   - 25p D.sub.34p -NH.sub.2 D.sub.34p                                                              #STR67##                                                   - 25q D.sub.34q -NH.sub.2 D.sub.34q                                                              #STR68##                                                   - 25r D.sub.34r -NH.sub.2 D.sub.34r                                                              #STR69##                                                   - 26 D.sub.35 -NH.sub.2 D.sub.35 =                                                               #STR70##                                                   - 27 D.sub.36 -NH.sub.2 D.sub.36 =                                                               #STR71##                                                   - 28 D.sub.37 -NH.sub.2 D.sub.37 =                                                               #STR72##                                                   - 29 D.sub.38 -NH.sub.2 D.sub.38 =                                                               #STR73##                                                   - 30 D.sub.39 -NH.sub.2 D.sub.39 =                                                               #STR74##                                                   - 31 D.sub.40a -NH.sub.2 -D.sub.40f -NH.sub.2 D.sub.40a -D.sub.40f =                             #STR75##                                                   -                                                                          T.sub.3 :                                                                       31a D.sub.40a -NH.sub.2 D.sub.40a                                                                 #STR76##                                                   - 31b D.sub.40b -NH.sub.2 D.sub.40b                                                              #STR77##                                                   - 31c D.sub.40c -NH.sub.2 D.sub.40c                                                              #STR78##                                                   - 31d D.sub.40d -NH.sub.2 D.sub.40d                                                              #STR79##                                                   - 31e D.sub.40e -NH.sub.2 D.sub.40a                                                              #STR80##                                                   - 31f D.sub.40f -NH.sub.2 D.sub.40f                                                              #STR81##                                                   - 32 D.sub.41a -NH.sub.2 -D.sub.41u -NH.sub.2 D.sub.41a -D.sub.41u =                             #STR82##                                                   - 33 D.sub.42a -NH.sub.2 -D.sub.42u -NH.sub.2 D.sub.42a -D.sub.42u =                             #STR83##                                                   -                                                                          D:                                                                              32a/33a D.sub.41a/42a -NH.sub.2 D.sub.41a/42a                                                     #STR84##                                                   - 32b/33b D.sub.41b/42b -NH.sub.2 D.sub.41b/42b                                                  #STR85##                                                   - 32c/33c D.sub.41c/42c -NH.sub.2 D.sub.41c/42c                                                  #STR86##                                                   - 32d/33d D.sub.41d/42d -NH.sub.2 D.sub.41d/42d                                                  #STR87##                                                   - 32e/33e D.sub.41e/42e -NH.sub.2 D.sub.41e/42e                                                  #STR88##                                                   - 32f/33f D.sub.41f/42f -NH.sub.2 D.sub.41f/42f                                                  #STR89##                                                   - 32g/33g D.sub.41g/42g -NH.sub.2 D.sub.41g/42g                                                  #STR90##                                                   - 32h/33h D.sub.41h/42h -NH.sub.2 D.sub.41h/42h                                                  #STR91##                                                   - 32i/33i D.sub.41i/42i -NH.sub.2 D.sub.41i/42i                                                  #STR92##                                                   - 32j/33j D.sub.41j/42j -NH.sub.3 D.sub.41j/42j                                                  #STR93##                                                   - 32k/33k D.sub.41k/42k -NH.sub.2 D.sub.41k/42k                                                  #STR94##                                                   - 32l/33l D.sub.41l/42l -NH.sub.2 D.sub.41l/42l                                                  #STR95##                                                   - 32m/33m D.sub.41m/42m -NH.sub.2 D.sub.41m/42m                                                  #STR96##                                                   - 32n/33n D.sub.41n/42n -NH.sub.2 D.sub.41n/42n                                                  #STR97##                                                   - 32o/33o D.sub.41o/42o -NH.sub.2 D.sub.41o/42o                                                  #STR98##                                                   - 32p/33p D.sub.41p/42p -NH.sub.2 D.sub.41p/42p                                                  #STR99##                                                   - 32q/33q D.sub.41q/42q -NH.sub.2 D.sub.41q/42q                                                  #STR100##                                                  - 32r/33r D.sub.41r/42r -NH.sub.2 D.sub.41r/42r                                                  #STR101##                                                  - 32s/33s D.sub.41s/42s -NH.sub.2 D.sub.41s/42s                                                  #STR102##                                                  - 32t/33t D.sub.41t/42t -NH.sub.2 D.sub.41t/42t                                                  #STR103##                                                  - 32u/33u D.sub.41u/42u -NH.sub.2 D.sub.41u/42u                                                 ##STR104##                                               __________________________________________________________________________

EXAMPLE 34 16 parts of the diamine of the formula H₂ N--D₄₃ --NH₂, inwhich D₄₃ is a radical of the formula ##STR105## are dissolved in 160parts of water under neutral conditions. 13 parts of concentratedhydrochloric acid and then 19.5 parts of a 4N sodium nitrite solutionare slowly added at 0° C. When the diamine has reacted to give thecorresponding tetrazo compound, the excess nitrite is destroyed byaddition of sulfamic acid. EXAMPLES 35 to 37

The tetrazo compounds of the diamines listed in Table 2 can be preparedanalogously to the procedure described in Example 34 if an equimolaramount of the diamines of the formula H₂ N--D_(xy) --NH₂ listed in Table2 is used in place of the diamine of the formula H₂ N--D₄₃ --NH₂mentioned in Example 34.

                                      TABLE 2                                     __________________________________________________________________________       Diamine                                                                      Exp. H.sub.2 N-D.sub.xy -NH.sub.2 D.sub.xy                                  __________________________________________________________________________      35 H.sub.2 N-D.sub.44 -NH.sub.2 D.sub.44 =                                                 #STR106##                                                         - 36 H.sub.2 N-D.sub.45 -NH.sub.2 D.sub.45 =                                              #STR107##                                                         - 37 H.sub.2 N-D.sub.46 -NH.sub.2 D.sub.46 =                                             ##STR108##                                                      __________________________________________________________________________

EXAMPLE 38

a) 1st coupling: a solution of 15.2 parts of 3,5-diaminobenzoic acid in100 parts of 2N hydrochloric acid is added at 0 to 5° C. to the aciddiazo compound suspension obtained according to Example 1. The pH of thereaction mixture is brought to 3.2 in the course of 4 hours with a 40%sodium acetate solution. The mixture is then stirred at 6 to 7° C. for afurther 30 minutes. A compound which, in the form of the free acid, hasthe formula (101) ##STR109## is obtained.

b) 2nd coupling: the acid diazo compound suspension obtained accordingto Example 2 is added at 7° C. and pH 3.2 to the suspension, obtainedaccording to a), of the compound of the formula (101). The pH of thereaction mixture is brought to 3.5 in the course of 45 minutes at 12 to15° C. with a 40% sodium acetate solution and to 6.3 in the course of 1hour at 15 to 19° C. with sodium bicarbonate. The mixture is thenstirred at about 25° C. for a further 45 minutes. The resulting solutionis treated with 450 parts of acetone, the pH is brought to 1.5 withconcentrated hydrochloric acid and 4.6 parts of potassium chloride areadded. The dye which has precipitated out is filtered off and washedwith acetone. 70.1 parts of a compound which, in the form of the freeacid, has the formula (102) ##STR110## and dyes cotton and wool inorange colour shades with good allround properties are obtained.

EXAMPLES 39 to 108

The dyes of the following general formula (103) ##STR111## in which D¹_(xy) and D² _(xy) in each case are the radicals listed in Table 3 andthese radicals are as defined in Examples 1 and 2 and in Table 1 can beprepared from the diazo compounds described in Examples 1 to 33analogously to the procedure described in Example 38. The dyes dyecotton and wool in the colour shades stated in Table 3 with goodallround properties.

                  TABLE 3                                                         ______________________________________                                               D.sup.1.sub.xy                                                                             D.sup.2.sub.xy                                              Exp. 1st coupling 2nd coupling Colour shade                                 ______________________________________                                        39     D.sub.10     D.sub.12  orange                                            40 D.sub.13 D.sub.11 orange                                                   41 D.sub.13 D.sub.12 orange                                                   42 D.sub.10 D.sub.13 orange                                                   43 D.sub.10 D.sub.14 orange                                                   44 D.sub.10 D.sub.15 orange                                                   45 D.sub.10 D.sub.16 orange                                                   46 D.sub.10 D.sub.17 orange                                                   47 D.sub.10 D.sub.18 orange                                                   48 D.sub.10 D.sub.32 orange                                                   49 D.sub.10 D.sub.33 orange                                                   50 D.sub.10 D.sub.19 orange                                                   51 D.sub.10 D.sub.20 orange                                                   52 D.sub.10 D.sub.21 orange                                                   53 D.sub.10 D.sub.22 orange                                                   54 D.sub.10 D.sub.29 orange                                                   55 D.sub.30 D.sub.11 orange                                                   56 D.sub.30 D.sub.12 orange                                                   57 D.sub.30 D.sub.13 orange                                                   58 D.sub.30 D.sub.14 orange                                                   59 D.sub.30 D.sub.15 orange                                                   60 D.sub.30 D.sub.16 orange                                                   61 D.sub.30 D.sub.17 orange                                                   62 D.sub.30 D.sub.18 orange                                                   63 D.sub.30 D.sub.19 orange                                                   64 D.sub.30 D.sub.20 orange                                                   65 D.sub.30 D.sub.21 orange                                                   66 D.sub.30 D.sub.22 orange                                                   67 D.sub.30 D.sub.29 orange                                                   68 D.sub.31 D.sub.11 orange                                                   69 D.sub.38 D.sub.11 brown                                                    70 D.sub.10 D.sub.23 orange                                                   71 D.sub.10 D.sub.24 orange                                                   72 D.sub.10 D.sub.25 orange                                                   73 D.sub.10 D.sub.26 orange                                                   74 D.sub.10 D.sub.27 orange                                                   75 D.sub.10 D.sub.28 orange                                                   76 D.sub.34a D.sub.13 brown-orange                                            77 D.sub.34b D.sub.13 brown-orange                                            78 D.sub.34c D.sub.13 brown-orange                                            79 D.sub.34d D.sub.13 brown-orange                                            80 D.sub.34e D.sub.13 brown-orange                                            81 D.sub.34f D.sub.13 brown-orange                                            82 D.sub.34g D.sub.13 brown-orange                                            83 D.sub.34h D.sub.13 brown-orange                                            84 D.sub.34i D.sub.13 brown-orange                                            85 D.sub.34j D.sub.13 brown-orange                                            86 D.sub.34k D.sub.13 brown-orange                                            87 D.sub.34l D.sub.13 brown-orange                                            88 D.sub.34m D.sub.13 brown-orange                                            89 D.sub.34n D.sub.13 brown-orange                                            90 D.sub.34o D.sub.13 brown-orange                                            91 D.sub.34p D.sub.13 brown-orange                                            92 D.sub.34q D.sub.13 brown-orange                                            93 D.sub.34r D.sub.13 brown-orange                                            94 D.sub.35 D.sub.13 brown-orange                                             95 D.sub.36 D.sub.13 brown-orange                                             96 D.sub.37 D.sub.13 brown-orange                                             97 D.sub.35 D.sub.11 brown-orange                                             98 D.sub.36 D.sub.11 brown-orange                                             99 D.sub.37 D.sub.11 brown-orange                                             100  D.sub.34a D.sub.11 brown-orange                                          101  D.sub.34e D.sub.11 brown-orange                                          102  D.sub.34f D.sub.11 brown-orange                                          103  D.sub.34g D.sub.11 brown-orange                                          104  D.sub.34h D.sub.11 brown-orange                                          105  D.sub.39 D.sub.13 brown                                                  106  D.sub.39 D.sub.11 brown                                                  107  D.sub.40a D.sub.13 brown-orange                                          108  D.sub.40a D.sub.11 brown-orange                                        ______________________________________                                    

EXAMPLE 109

a) 1st coupling: a solution of 15.2 parts of 3,5-diaminobenzoic acid in100 parts of 2N hydrochloric acid is added at 0 to 5° C. to the acidtetrazo compound suspension obtained according to Example 34. The pH ofthe reaction mixture is brought to 3.2 in the course of 4 hours with a40% sodium acetate solution. The mixture is then stirred at 6 to 7° C.for a further 30 minutes. A compound which, in the form of the freeacid, has the formula (104) ##STR112## is obtained.

b) 2nd coupling: the acid diazo compound suspension obtained accordingto Example 2 is added at 7° C. and pH 3.2 to the suspension, obtainedaccording to a), of the compound of the formula (104). The pH of thereaction mixture is brought to 3.5 in the course of 45 minutes at 12 to15° C. with a 40% sodium acetate solution and to 6.3 in the course ofone hour at 15 to 19° C. with sodium bicarbonate. The mixture is thenstirred at about 25° C. for a further 45 minutes. 450 parts of acetoneare added to the resulting solution, the pH is brought to 1.5 withconcentrated hydrochloric acid and 4.6 parts of potassium chloride areadded. The dye which has precipitated out is filtered off and washedwith acetone. 68 parts of a compound which, in the form of the freeacid, has the formula (105) ##STR113## and dyes cotton and wool inbrown-orange colour shades with good allround properties are obtained.

EXAMPLES 110 to 113

The dyes of the following general formula (106) ##STR114## in which D¹_(xy) and D² _(xy) in each case are the radicals listed in Table 4 andthese radicals are as defined in Table 2 and in Examples 2 and 4, can beprepared from the tetrazo compounds described in Table 2 and the diazocompounds described in Examples 2 and 4 analogously to the proceduredescribed in Example 109. The dyes dye cotton and wool in the colourshades stated in Table 4 with good allround properties.

                  TABLE 4                                                         ______________________________________                                               D.sup.1.sub.xy                                                                             D.sup.2.sub.xy                                              Exp. 1st coupling 2nd coupling Colour shade                                 ______________________________________                                        110    D.sub.44     D.sub.13  brown-orange                                      111 D.sub.45 D.sub.13 brown-orange                                            112 D.sub.46 D.sub.13 brown-orange                                            113 D.sub.46 D.sub.11 brown-orange                                          ______________________________________                                    

EXAMPLE 114

A solution of 10.1 parts of 3,5-diaminobenzoic acid in 67 parts of 2Nhydrochloric acid is added at 0 to 5° C. to the acid diazo compoundsuspension obtained according to Example 2. The pH of the reactionmixture is brought to 3.2 in the course of one hour with a 40% sodiumacetate solution, to 5.8 in the course of a further hour with sodiumbicarbonate and to 7.8 in the course of 45 minutes with a 20% sodiumcarbonate solution. The resulting solution is brought to pH 0.8 withconcentrated hydrochloric acid, and 80 parts of acetone and 112 parts ofpotassium chloride are added. The dye which has precipitated out isfiltered off and washed with acetone. 64.6 parts of a compound which, inthe form of the free acid, has the formula (107) ##STR115## and dyescotton and wool in orange colour shades with good allround propertiesare obtained.

EXAMPLES 115 to 140

The dyes of the general formula (108) ##STR116## in which D_(xy) in eachcase are the radicals listed in Table 5 and these radicals are asdefined in Table 1, can be obtained from the diazo compounds describedin Examples 3 to 5, 9 to 12, 14, 15, 20 and 23 to 25 analogously to theprocedure described in Example 114. The dyes dye cotton and wool in thecolour shades stated in Table 5 with good allround properties.

                  TABLE 5                                                         ______________________________________                                        Exp.          D.sub.xy                                                                             Colour shade                                             ______________________________________                                        115           D.sub.12                                                                             orange                                                     116 D.sub.13 orange                                                           117 D.sub.14 orange                                                           118 D.sub.18 orange                                                           119 D.sub.19 orange                                                           120 D.sub.20 orange                                                           121 D.sub.21 orange                                                           122 D.sub.23 orange                                                           123 D.sub.24 orange                                                           124 D.sub.29 orange                                                           125 D.sub.32 orange                                                           126 D.sub.33 orange                                                           127 D.sub.34a orange                                                          128 D.sub.34b orange                                                          129 D.sub.34c orange                                                          130 D.sub.34e orange                                                          131 D.sub.34f orange                                                          132 D.sub.34g orange                                                          133 D.sub.34i orange                                                          134 D.sub.34j orange                                                          135 D.sub.34l orange                                                          136 D.sub.34m orange                                                          137 D.sub.34n orange                                                          138 D.sub.34o orange                                                          139 D.sub.34q orange                                                          140 D.sub.34r orange                                                        ______________________________________                                    

EXAMPLE 141

14.4 parts of 2-sulfo-4-(β-sulfatoethylsulfonyl)aniline and 22.7 partsof 4-(β-sulfatoethylsulfonyl)aniline are introduced into 120 parts ofwater and the mixture is stirred thoroughly. First 30 parts of a 4Nsodium nitrite solution and then 50 parts of a 31% naphthalenesulfonicacid solution are added to the resulting suspension at 10° C. Themixture is then stirred at 15 to 20 C. for 3 hours. A solution of 6.1parts of 3,5-diaminobenzoic acid in 40 parts of 2N hydrochloric acid isadded to this suspension at 0 to 5° C. The pH of the reaction mixture isbrought to 3.2 in the course of one hour at 0 to 5° C. with a 40% sodiumacetate solution, to 5.8 in the course of a further hour with sodiumbicarbonate and to 7.8 in the course of 45 minutes with a 20% sodiumcarbonate solution. The resulting solution is evaporated. 66.9 parts ofa product which essentially comprises a mixture of compounds which, inthe form of the free acid, have the formulae (109), (110), (111), (112),(113) and (114) ##STR117## in which D₁₁, and D₁₃ are as defined inExamples 2 and 4, are obtained. The dye mixture dyes cotton and wool inorange colour shades with good allround properties.

EXAMPLE 142

a) 22.3 parts of 2-aminonaphthalenesulfonic acid are introduced into 215parts of water and the mixture is stirred thoroughly. 25 parts of a 4Nsodium nitrite solution are added to the resulting solution at 0° C. and20 parts of concentrated hydrochloric acid are then slowly addeddropwise at 0 to 5° C. The mixture is stirred at this temperature for 1hour.

b) 30.3 parts of 2-amino-1,5-naphthalenedisulfonic acid are introducedinto 215 parts of water and the mixture is stirred thoroughly. 25 partsof a 4N sodium nitrite solution are added to the resulting solution at0° C. and 20 parts of concentrated hydrochloric acid are then slowlyadded dropwise at 0 to 5° C. The mixture is stirred at this temperaturefor 1 hour.

c) 28.1 parts of 4-(β-sulfatoethylsulfonyl)aniline are introduced into110 parts of water and the mixture is stirred thoroughly. First 25 partsof a 4N sodium nitrite solution and then 45 parts of a 31%naphthalenesulfonic acid solution are added to the resulting suspensionat 10° C. The mixture is then stirred at 15 to 20° C. for 3 hours.

d) 1st coupling: a solution 15.2 parts of 3,5-diaminobenzoic acid in 100parts of 2N hydrochloric acid is added at 0 to 5° C. to the acid diazocompound suspension obtained according to a). The pH of the reactionmixture is brought to 3.2 in the course of 4 hours with a 40% sodiumacetate solution. The mixture is then stirred at 6 to 7° C. for afurther 30 minutes.

e) 2nd coupling: the acid diazo compound suspension obtained accordingto b) is added at 7° C. and pH 3.2 to the suspension obtained accordingto d). The pH of the reaction mixture is brought to 4.5 in the course of45 minutes with a 40% sodium acetate solution. The mixture is thenstirred at about 15° C. for a further 30 minutes.

f) 3rd coupling: the acid diazo compound suspension obtained accordingto c) is added at 15° C. and pH 4.5 to the suspension obtained accordingto e). The pH of the reaction mixture is brought to 6.3 in the course ofone hour with sodium bicarbonate. The mixture is then stirred at about25° C. for a further 45 minutes. 450 parts of acetone are added to theresulting solution, the pH is brought to 1.5 with concentratedhydrochloric acid and 4.6 parts of potassium chloride are added. Theproduct which has precipitated out is filtered off and washed withacetone. 72 parts of a product which essentially comprises a compoundwhich, in the form of the free acid, has the formula (115) ##STR118##and dyes cotton and wool in orange colour shades with good allroundproperties are obtained.

EXAMPLES 143 to 192

Dyes which essentially comprise a compound of the following generalformula (116) ##STR119## in which D¹ _(xy), D² _(xy) and D³ _(xy) ineach case are the radicals listed in Table 6 and these radicals are asdefined in Example 2 and Table 1, can be prepared from the diazocompounds described in Examples 2, 4 and 29 to 33 analogously to theprocedure described in Example 142. The dyes dye cotton and wool in thecolour shades stated in Table 6 with good allround properties.

                  TABLE 6                                                         ______________________________________                                              D.sup.1.sub.xy                                                                          D.sup.2.sub.xy                                                                           D.sup.3.sub.xy                                       Exp. 1st coupling 2nd coupling 3rd coupling Colour shade                    ______________________________________                                        143   D.sub.38  D.sub.11   D.sub.13                                                                              brown                                        144 D.sub.39 D.sub.11 D.sub.13 brown                                          145 D.sub.4Oa D.sub.11 D.sub.13 brown-orange                                  146 D.sub.40b D.sub.11 D.sub.13 gold-orange                                   147 D.sub.40c D.sub.11 D.sub.13 gold-orange                                   148 D.sub.40d D.sub.11 D.sub.13 gold-orange                                   149 D.sub.40e D.sub.11 D.sub.13 gold-yellow                                   150 D.sub.40f D.sub.11 D.sub.13 gold-yellow                                   151 D.sub.41a D.sub.11 D.sub.13 red                                           152 D.sub.41b D.sub.11 D.sub.13 red                                           153 D.sub.41c D.sub.11 D.sub.13 red                                           154 D.sub.4ld D.sub.11 D.sub.13 red                                           155 D.sub.41e D.sub.11 D.sub.13 red                                           156 D.sub.41f D.sub.11 D.sub.13 red                                           157 D.sub.41g D.sub.11 D.sub.13 red                                           158 D.sub.4lh D.sub.11 D.sub.13 red                                           159 D.sub.41i D.sub.11 D.sub.13 red                                           160 D.sub.41j D.sub.11 D.sub.13 red                                           161 D.sub.4lk D.sub.11 D.sub.13 red                                           162 D.sub.41l D.sub.11 D.sub.13 red                                           163 D.sub.41m D.sub.11 D.sub.13 red                                           164 D.sub.41n D.sub.11 D.sub.13 red                                           165 D.sub.41o D.sub.11 D.sub.13 red                                           166 D.sub.41p D.sub.11 D.sub.13 red                                           167 D.sub.41q D.sub.11 D.sub.13 red                                           168 D.sub.41r D.sub.11 D.sub.13 red                                           169 D.sub.41s D.sub.11 D.sub.13 red                                           170 D.sub.41t D.sub.11 D.sub.13 red                                           171 D.sub.41u D.sub.11 D.sub.13 red                                           172 D.sub.42a D.sub.11 D.sub.13 orange                                        173 D.sub.42b D.sub.11 D.sub.13 orange                                        174 D.sub.42c D.sub.11 D.sub.13 orange                                        175 D.sub.42d D.sub.11 D.sub.13 orange                                        176 D.sub.42e D.sub.11 D.sub.13 orange                                        177 D.sub.42f D.sub.11 D.sub.13 orange                                        178 D.sub.42g D.sub.11 D.sub.13 orange                                        179 D.sub.42h D.sub.11 D.sub.13 orange                                        180 D.sub.42i D.sub.11 D.sub.13 orange                                        181 D.sub.42j D.sub.11 D.sub.13 orange                                        182 D.sub.42k D.sub.11 D.sub.13 orange                                        183 D.sub.42l D.sub.11 D.sub.13 orange                                        184 D.sub.42m D.sub.11 D.sub.13 orange                                        185 D.sub.42n D.sub.11 D.sub.13 orange                                        186 D.sub.42o D.sub.11 D.sub.13 orange                                        187 D.sub.42p D.sub.11 D.sub.13 orange                                        188 D.sub.42q D.sub.11 D.sub.13 orange                                        189 D.sub.42r D.sub.11 D.sub.13 orange                                        190 D.sub.42s D.sub.11 D.sub.13 orange                                        191 D.sub.42t D.sub.11 D.sub.13 orange                                        192 D.sub.42u D.sub.11 D.sub.13 orange                                      ______________________________________                                    

The procedure described in Examples 38 to 108 and 114 to 192 isrepeated, except that an equimolar amount of the compound of the formula(117), (118), (119), (120) or (121) ##STR120## is used in place of3,5-diaminobenzoic acid. Further valuable dyes which dye cotton and woolwith good allround properties can be prepared.

The procedure described in one of Examples 109 to 113 is repeated,except that an equimolar amount of the compound of the formula (117),(118) or (119) is used in place of 3,5-diaminobenzoic acid. Valuabledyes which dye cotton and wool with good allround properties canlikewise be prepared.

The compounds of the formulae (117), (118), (119), (120) and (121) areknown or can be prepared analogously to known compounds.

Dyeing Instructions I

100 parts of cotton fabric are introduced at 60° C. into 1500 parts of adyebath which comprises 45 g/l of sodium chloride and 2 parts of thereactive dye obtained according to Example 38. After 45 minutes at 60°C., 20 g/l of calcined sodium carbonate are added. Dyeing is continuedat this temperature for a further 45 minutes. Thereafter, the dyed goodsare rinsed, soaped at the boil with a nonionic detergent for a quarterof an hour, rinsed again and dried.

As an alternative to the instructions given, dyeing can also be carriedout at 80° C. instead of at 60° C.

Dyeing Instructions II

0.1 part of the dye according to Example 38 is dissolved in 200 parts ofwater, and 0.5 part of sodium sulfate, 0.1 part of a levelling assistant(based on the condensation product of a higher aliphatic amine andethylene oxide) and 0.5 part of sodium acetate are added. The pH is thenbrought to a value of 5.5 with acetic acid (80%). The dyebath is heatedto 50° C. for 10 minutes and 10 parts of a woollen fabric are thenadded. The bath is heated to a temperature of 100° C. in the course ofabout 50 minutes and dyeing is carried out at this temperature for 60minutes. Thereafter, the bath is allowed to cool to 90° C. and the dyedgoods are removed. The woollen fabric is washed with warm and cold waterand then spun and dried.

Printing Instructions

3 parts of the dye obtained according to Example 141 are sprinkled withrapid stirring into 100 parts of a stop thickener comprising 50 parts of5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodiumbicarbonate. A cotton fabric is printed with the printing paste thusobtained, dried, and the resulting printed material is steamed insaturated steam at 102° C. for 2 minutes. The printed fabric is thenrinsed, can be soaped at the boil and rinsed again, and is then dried.

What is claimed is:
 1. An azo dye containing at least one structuralunit of the formula (1) ##STR121##
 2. An azo dye according to claim 1,which has the formula (2), (3) or (4) in whichA is oxygen, sulfur or aradical --NR'-- and R' is hydrogen or C₁ -C₁₂ alkyl which is substitutedor unsubstituted or may be interrupted by oxygen, B is an aliphatic oraromatic bridge member, D₁, D₂ and D₃ independently of one another areeach the radical of a diazo component of the benzene or naphthaleneseries, D₄ is the radical of an aromatic tetrazo component and R ishydrogen or an aliphatic or aromatic radical, or the radicals R and R',together with the nitrogen atom, form a heterocyclic radical.
 3. An azodye according to claim 2, in whichA is oxygen or a radical --NR'--. 4.An azo dye of the formula (2) or (4) according to claim 2, in whichA isoxygen and R is hydrogen.
 5. An azo dye according to claim 2, which hasthe formula (2).
 6. An azo dye according to claim 2, in whichD₁, D₂ andD₃ independently of one another are each a radical of the formula (15)or (16) ##STR122## in which K is the radical of a coupling component ofthe formula (17a) or (17b) ##STR123## and Z and Z₁ independently of oneanother are a radical of the formula (6a), (6c), (6d), (6e) or (6f)

    --SO.sub.2 --Y                                             (6a),

    --CONR.sub.2 --(CH.sub.2).sub.m --SO.sub.2 --Y             (6c),

    --NH--CO--CH(Hal)--CH.sub.2 --Hal                          (6d),

    --NH--CO--C(Hal)═CH.sub.2                              ( 6e), ##STR124## in which R.sub.1a and R.sub.2 are hydrogen,

Hal is bromine, Y is vinyl, β-chloroethyl or β-sulfatoethyl, T₁ is C₁-C₄ alkoxy, C₁ -C₄ alkylthio, hydroxyl, amino, N-mono- or N,N-di-C₁ -C₄alkylamino which are unsubstituted or substituted in the alkyl moiety byhydroxyl, sulfato or sulfo, morpholino, phenylamino or N--C₁ -C₄alkyl-N-phenylamino which are unsubstituted or substituted in the phenylring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and inwhich the alkyl is unsubstituted or substituted by hydroxyl, sulfo orsulfato, naphthylamino which is unsubstituted or substituted by 1 to 3sulfo groups, or a fibre-reactive radical of the formula (7c') or (7d')##STR125## and Y is as defined above, X₁ is chlorine or fluorine, m isthe number 2 or 3, (R₄)₀₋₃ and (R₁₃)₀₋₃ independently of one another are0 to 3 identical or different substituents chosen from the groupconsisting of halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, carboxyl and sulfo,R'₅ is hydrogen, sulfo or C₁ -C₄ alkoxy which is unsubstituted orsubstituted in the alkyl moiety by hydroxyl or sulfato and R'_(5a) ishydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, ureido or aradical of the formula (6f), in which radicals R_(1a), T₁ and X₁ are asdefined above.
 7. An azo dye according to claim 6, in whichthe radicalsD₁, D₂ and D₃ independently of one another are each a radical of theformula (15a), (15b), (15c), (15d) or (16a) ##STR126## in which R'₅ ishydrogen, sulfo or ethoxy which is unsubstituted or substituted in thealkyl moiety by hydroxyl or sulfato, R'_(5a) is hydrogen, methyl, ethyl,methoxy, ethoxy, acetylamino, propionylamino or ureido, (R₁₃)₀₋₂ is 0 to2 identical or different substituents chosen from the group consistingof halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy and sulfo, Y₁ is a group--CH(Br)--CH₂ --Br or --C(Br)═CH₂, Y is vinyl, β-chloroethyl orβ-sulfatoethyl and m is the number 2 or
 3. 8. An azo dye according toclaim 2, in whichD₁ is a radical of the formula (18) ##STR127## in whichX₁ is chlorine or fluorine and T₃ is a radical of the formula (10a),(10b), (10d), (10e), (10f), (10k) or (10m) ##STR128## in which (R₄)₀₋₃is 0 to 3 identical or different substituents from the group consistingof C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxyl and sulfo, (R₅)₀₋₃ is0 to 3 identical or different substituents from the group consisting ofhalogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ -C₄alkyl, C₁ -C₄ alkoxy which is unsubstituted or substituted by hydroxyl,sulfato or C₁ -C₄ alkoxy, amino, C₂ -C₄ alkanoylamino, ureido, hydroxyl,carboxyl, sulfomethyl, C₁ -C₄ alkylsulfonylamino and sulfo, R₈ and R₁₀independently of one another are hydrogen, C₁ -C₄ alkyl or phenyl and R₉is hydrogen, cyano, carbamoyl or sulfomethyl, (R₁₁)₀₋₃ is 0 to 3identical or different substituents from the group consisting of C₁ -C₄alkyl, C₁ -C₄ alkoxy, halogen, carboxyl and sulfo and Z₁ is a radical ofthe formula (6a), (6c'), (6d') or (6e')

    --SO.sub.2 --Y                                             (6a),

    --CONH--(CH.sub.2).sub.2-3 --SO.sub.2 --Y                  (6c'),

    --NH--CO--CH(Br)--CH.sub.2 --Br                            (6d')

or

    --NH--CO--C(Br)═CH.sub.2                               ( 6e')

in which Y is vinyl, β-chloroethyl or β-sulfatoethyl; and the radicalsD₂ and D₃ independently of one another are each a radical of the formula(15a), (15b), (15c) or (15d) ##STR129## in which (R₁₃)₀₋₂ is 0 to 2identical or different substituents chosen from the group consisting ofhalogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy and sulfo, Y₁ is a group--CH(Br)--CH₂ --Br or --C(Br)═CH₂, Y is as defined above and m is thenumber 2 or
 3. 9. An azo dye according to claim 7, which has the formula(2a) ##STR130## in which D₁, D₂ and D₃ independently of one another ineach case are a radical of the formula (15a), (15b), (15c), (15d) or(16a) where at least one of the radicals D₁, D₂ and D₃ contains afibre-reactive group.
 10. An azo dye according to claim 8, which has theformula (2a) ##STR131## in which D₁ is a radical of the formula (18), inwhichX₁ is chlorine and T₃ is a radical of the formula (10a), (10b),(10d), (10e), (10f), (10k) or (10m) and D₂ and D₃ independently of oneanother in each case are a radical of the formula (15a), (15b), (15c) or(15d) where at least one of the radicals D₂ and D₃ contains afibre-reactive group.
 11. A process for the preparation of an azo dyeaccording to claim 1, which comprises coupling one or more than onediazotized amine together or in any sequence to a compound containing atleast one structural unit of the formula (19) ##STR132## such that anazo dye which contains at least one structural unit of the formula (1)is obtained.
 12. A process for dyeing or printing a fibre materialcontaining hydroxyl groups or nitrogen, which comprises applying to saidfibre material an azo dye of formula (1) according to claim
 1. 13. Aprocess according to claim 12, wherein said fibre material is cellulosicfibre material.
 14. A process according to claim 12, wherein said fibrematerial is cotton.